Considerable quantities of relatively high molecular weight, crosslinked, secondary products are formed in the production of isocyanates on an industrial scale. These secondary products are obtained as tar-like, non-distillable residues during the working up by distillation, of the crude isocyanate solutions obtained in the phosgenation of amines. These residues cannot be used as such for the conventional applications of polyisocyanates (production of polyurethane plastics). In order to avoid a total loss of the non-distillable residue, it is possible in some cases (for example in the phosgenation of diamines of the diphenyl methane series) to isolate only part of the pure monomeric isocyanate from the crude phosgenation product, i.e. to leave a considerable proportion of monomeric isocyanate in the sump phase, in order to obtain the relatively high molecular weight secondary products in solution. For the liquid polyisocyanate mixture enriched with relatively high molecular weight products obtained in this way (so-called "crude MDI"), it has been possible in recent years to find a number of potential applications in special polyurethane plastics.
All attempts, however, to use tolylene diisocyanate enriched with relatively high molecular weight secondary products ("crude TDI") and having a low, but still economically acceptable content of monomeric tolylene diisocyanate have so far failed. During distillation of the phosgenation product of tolylene diamines, relatively high molecular weight insoluble products containing uretdione, isocyanurate, carbodiimide, uretone imine, urea and biuret groups are formed under the conditions used in practice. Depending on the o-tolylene diamine content of the starting product, methyl benzimidazolones can also be formed during phosgenation and, with time, are biuretized with the free isocyanate groups present, accompanied by formation of insoluble, cross-linked products. Although crude TDI distillation residues which still have a high monomer content (greater than 80% by weight) and contain virtually no methyl benzimidazolone or its derivatives, are soluble or liquid, they are insufficiently stable in storage. The content of free NCO-groups decreases during storage, even at room temperature, accompanied by an increase in viscosity.
Numerous processes have also been proposed (U.S. Pat. No. 3,634,361; German Offenlegungsschrift No. 2,123,183; German Offenlegungsschrift No. 2,333,150; U.S. Pat. No. 3,455,836 and German Offenlegungsschrift No. 2,423,594) for dissolving TDI distillation residues which still have a considerable content of free NCO-groups (preferably greater than 20% by weight), in an organic solvent in the presence of monomeric diisocyanates, optionally at a high temperature, and for using these residue solutions as the isocyanate component in the polyisocyanate polyaddition process. In practice, however, this method of utilizing the TDI residues fails because of the inadequate stability during storage and the inability to standardize the solutions (if in fact dissolutions were possible at all) or because of the sedimentation of insoluble constituents.
In recent years, TDI distillation residues have been partly utilized by means of alkaline hydrolysis. Unfortunately, only relatively small proportions of tolylene diamines can be recovered.
More success in maximizing the TDI yield has been achieved by so-called long-tube vertical evaporators (U.S. Pat. No. 3,897,314), which has been adopted for use on a wide scale in the commercial production of tolylene diisocyanate, and mixtures of 2,4- and 2,6-tolylene diisocyanate and by continuous thermolysis of the liquid TDI residue tar. In the above process, the residue is substantially free from monomers, but still contains free isocyanate groups. This residue has to be stirred into water (quenching) in the form of a hot (approximately 150.degree. to 300.degree. C.) tar-like mass immediately after separation of the pure monomeric TDI in order to avoid smoldering fires and for physiological reasons. During this quenching process, the majority of the free isocyanate groups still present react with the water to form additional polyurea groups (hereinafter called denaturing), this reaction being accompanied by the evolution of carbon dioxide. Thus, only a very small percentage, generally around 1 to 10% by weight, of included isocyanate groups are left unreacted. Storage in water or in moist form causes the isocyanate content to undergo a further gradual reduction over a prolonged period.
The slag-like TDI residues containing urea groups are substantially insoluble in all the conventional solvents. At temperatures above about 250.degree..+-.30.degree. C. they begin to melt to some extent, decomposing and giving off gases.
No commercially or economically interesting possibilities for utilizing these TDI-residue slags have yet been found.
The vast majority of TDI distillation residues accumulating in the production of TDI is either dumped or burned in furnaces with considerable difficulty. In cases where TDI residue slags are burned, deposits of firmly adhering, substantially incombustible tarry masses accumulate on the bottom of the combustion chamber and, in many cases, decompose explosively at temperatures above about 500.degree. C.
The object of the present invention is to provide commercially feasible possibilities for recycling TDI distillation residue slags, particularly the TDI residues slags denatured with water.